JP3127820B2 - Sputtering target for forming ferroelectric film and method for manufacturing the same - Google Patents
Sputtering target for forming ferroelectric film and method for manufacturing the sameInfo
- Publication number
- JP3127820B2 JP3127820B2 JP08040860A JP4086096A JP3127820B2 JP 3127820 B2 JP3127820 B2 JP 3127820B2 JP 08040860 A JP08040860 A JP 08040860A JP 4086096 A JP4086096 A JP 4086096A JP 3127820 B2 JP3127820 B2 JP 3127820B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- composite oxide
- sputtering target
- ferroelectric film
- forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005477 sputtering target Methods 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 5
- 239000000843 powder Substances 0.000 claims description 113
- 239000002131 composite material Substances 0.000 claims description 47
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 17
- 238000007731 hot pressing Methods 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 9
- 238000003754 machining Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- HFNQLYDPNAZRCH-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O.OC(O)=O HFNQLYDPNAZRCH-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910015802 BaSr Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Semiconductor Memories (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Description
【0001】[0001]
【発明の属する技術分野】この発明は、半導体メモリー
などのキャパシタ用薄膜成形のための強誘電体膜形成用
スパッタリングターゲットおよびその製造方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sputtering target for forming a ferroelectric film for forming a thin film for a capacitor such as a semiconductor memory, and a method for manufacturing the same.
【0002】[0002]
【従来の技術】一般に、BaおよびTiの複合酸化物
(以下、BaTi複合酸化物という)、SrおよびTi
の複合酸化物(以下、SrTi複合酸化物という)並び
にBa、SrおよびTiの複合酸化物(以下、BaSr
Ti複合酸化物という)からなるペロブスカイト構造を
有する強誘電体膜形成用スパッタリングターゲットは、
半導体メモリー等に用いられるキャパシタ用薄膜形成用
スパッタリングターゲットとして用いることは知られて
いる。2. Description of the Related Art In general, a composite oxide of Ba and Ti (hereinafter referred to as a BaTi composite oxide), Sr and Ti
Composite oxide (hereinafter, referred to as SrTi composite oxide) and a composite oxide of Ba, Sr, and Ti (hereinafter, BaSr
A sputtering target for forming a ferroelectric film having a perovskite structure composed of a Ti composite oxide)
It is known to use as a sputtering target for forming a thin film for a capacitor used in a semiconductor memory or the like.
【0003】前記BaTi複合酸化物からなるペロブス
カイト構造を有する強誘電体膜形成用スパッタリングタ
ーゲットを製造するには、まず原料粉末のBaCO3 粉
末およびTiO2 粉末を所定の割合に配合し、ボールミ
ルに入れて混合し、得られた混合粉末をMgOルツボに
入れ、大気雰囲気中、温度:1200〜1350℃、3
〜10時間保持の条件で焼成し、ボールミルで粉砕する
ことによりBaTi複合酸化物粉末を作製する。得られ
たBaTi複合酸化物粉末にさらに前記条件の焼成およ
び粉砕を2回以上繰り返して施した後、圧力:150k
g/cm2 、温度:1200〜1350℃、0.5〜3
時間保持の条件でホットプレスする。前記ホットプレス
されたBaTi複合酸化物からなる焼結体は、機械加工
して所定のターゲット形状に仕上げられる。In order to manufacture a ferroelectric film-forming sputtering target having a perovskite structure made of the BaTi composite oxide, first, BaCO 3 powder and TiO 2 powder as raw material powders are mixed in a predetermined ratio and put into a ball mill. And the resulting mixed powder is placed in a MgO crucible, and in an air atmosphere, at a temperature of 1200 to 1350 ° C.,
It is fired under the condition of holding for 10 to 10 hours, and pulverized by a ball mill to produce a BaTi composite oxide powder. The obtained BaTi composite oxide powder is further subjected to firing and pulverization under the above conditions twice or more, and then the pressure is set to 150 k.
g / cm 2 , temperature: 1200-1350 ° C., 0.5-3
Hot press under the condition of holding time. The sintered body of the hot-pressed BaTi composite oxide is machined and finished to a predetermined target shape.
【0004】また、前記SrTi複合酸化物からなるペ
ロブスカイト構造を有する強誘電体膜形成用スパッタリ
ングターゲットを製造するには、原料粉末のSrCO3
粉末およびTiO2 粉末を所定の割合に配合し、ボール
ミルに入れて混合し、得られた混合粉末をMgOルツボ
に入れ、大気雰囲気中、温度:1200〜1350℃、
3〜10時間保持の条件で焼成し、ボールミルで粉砕す
ることによりSrTi複合酸化物粉末を作製する。得ら
れたSrTi複合酸化物粉末にさらに前記条件の焼成お
よび粉砕を2回以上繰り返して施した後、圧力:150
kg/cm2 、温度:1200〜1350℃、0.5〜
3時間保持の条件でホットプレスする。前記ホットプレ
スされたSrTi複合酸化物からなる焼結体は、機械加
工して所定のターゲット形状に仕上げられる。In order to produce a ferroelectric film-forming sputtering target having a perovskite structure made of the above-mentioned SrTi composite oxide, the raw material powder SrCO 3
The powder and the TiO 2 powder are blended in a predetermined ratio, put in a ball mill and mixed, and the obtained mixed powder is put in a MgO crucible, in an air atmosphere, at a temperature of 1200 to 1350 ° C.
The SrTi composite oxide powder is prepared by firing under the condition of holding for 3 to 10 hours and pulverizing with a ball mill. The obtained SrTi composite oxide powder was repeatedly fired and pulverized under the above conditions twice or more, and then subjected to a pressure of 150.
kg / cm 2 , temperature: 1200-1350 ° C., 0.5-
Hot pressing is performed for 3 hours. The sintered body made of the hot-pressed SrTi composite oxide is machined and finished to a predetermined target shape.
【0005】さらに、前記BaSrTi複合酸化物から
なるペロブスカイト構造を有する強誘電体膜形成用スパ
ッタリングターゲットを製造するには、原料粉末のSr
CO 3 粉末、BaCO3 粉末およびTiO2 粉末を所定
の割合に配合し、ボールミルに入れて混合し、得られた
混合粉末をMgOルツボに入れ、大気雰囲気中、温度:
1200〜1350℃、3〜10時間保持の条件で焼成
し、ボールミルで粉砕することによりBaSrTi複合
酸化物粉末を作製する。得られたBaSrTi複合酸化
物粉末にさらに前記条件の焼成および粉砕をを2回以上
繰り返して施した後、圧力:150kg/cm2 、温
度:1200〜1350℃、0.5〜3時間保持の条件
でホットプレスする。前記ホットプレスされたBaSr
Ti複合酸化物からなる焼結体は、機械加工して所定の
ターゲット形状に仕上がられる。Further, from the BaSrTi composite oxide,
For forming a ferroelectric film having a perovskite structure
In order to manufacture the sputtering target, the raw material powder Sr
CO ThreePowder, BaCOThreePowder and TiOTwoPrescribe powder
And mixed in a ball mill to obtain
The mixed powder is placed in a MgO crucible, and in an air atmosphere, at a temperature of:
Fired at 1200-1350 ° C for 3-10 hours
And pulverized with a ball mill to obtain a BaSrTi composite
An oxide powder is prepared. Obtained BaSrTi composite oxidation
Baking and pulverizing the product powder under the above conditions twice or more
After repeated application, pressure: 150 kg / cmTwo, Warm
Degree: 1200-1350 ° C, 0.5-3 hours holding condition
Hot press. The hot pressed BaSr
The sintered body composed of Ti composite oxide is machined
Finished to the target shape.
【0006】[0006]
【発明が解決しようとする課題】近年、半導体メモリー
の大量生産とコストダウンのために、高出力でスパッタ
リングし、高速成膜することにより短時間で強誘電体膜
を形成しょうとしている。しかし、従来の強誘電体膜形
成用スパッタリングターゲットを用いて成膜速度:10
0オングストローム/min.以上の高速スパッタリン
グ成膜を行うと、ターゲット表面が鱗片状に剥離した
り、ターゲット全体が割れてしまうことがあり、また1
00オングストローム/min.以上の高速スパッタリ
ング成膜を行うためには、ターゲットを高密度化してタ
ーゲットの強度および熱伝導度を上げる必要があるが、
従来の原料を用いてホットプレスによりターゲットを製
造すると、ホットプレス上がりで割れが発生しやすく、
製品の歩留まりが低かった。In recent years, for mass production and cost reduction of semiconductor memories, it has been attempted to form a ferroelectric film in a short time by sputtering at a high output and forming a film at a high speed. However, using a conventional sputtering target for forming a ferroelectric film, a film forming rate of 10
0 angstroms / min. When the high-speed sputtering film formation is performed, the target surface may peel off in a scale-like manner, or the entire target may be broken.
00 angstroms / min. In order to perform the above high-speed sputtering film formation, it is necessary to increase the density of the target and increase the strength and thermal conductivity of the target,
When a target is manufactured by hot pressing using conventional raw materials, cracks tend to occur due to hot press up,
Product yield was low.
【0007】[0007]
【課題を解決するための手段】そこで、本発明者らは、
高電力をかけて高速スパッタリング成膜しても割れおよ
び剥離が生ずることがなく、さらにスパッタリングター
ゲット製造時の割れが発生せすることのない強誘電体膜
形成用スパッタリングターゲットを開発すべく研究を行
なった結果、(a)従来の強誘電体膜形成用スパッタリ
ングターゲットには、硫黄成分が80〜200ppm程
度含まれており、前記高速スパッタリング成膜時の割れ
および剥離は、硫黄成分が大きく影響を及ぼすところか
ら、強誘電体膜形成用スパッタリングターゲットに含ま
れる硫黄成分は可及的に少ない方がよく、S:50pp
m以下に抑える必要がある、(b)従来の強誘電体膜形
成用スパッタリングターゲットの原料粉末として用いる
市販の炭酸Ba粉末および炭酸Sr粉末には、硫黄成分
が80ppm以上含まれており、この硫黄成分が80p
pm以上含まれている炭酸Ba粉末および炭酸Sr粉末
を用いて強誘電体膜形成用スパッタリングターゲットを
製造すると、スパッタリングターゲット製造時のホット
プレス上がりで割れが発生するところから、原料粉末に
含まれる硫黄成分は、可及的に少ない方がよく、S:5
0ppm以下に抑える必要がある、(c)市販の酸化T
i粉末に含まれる硫黄含有量は、極めて少なく、5pp
m以下であるところから、市販の酸化Ti粉末をそのま
ま原料粉末として使用することができる、という知見を
得たのである。Means for Solving the Problems Accordingly, the present inventors have:
Conducted research to develop a sputtering target for ferroelectric film formation that does not cause cracking and peeling even when high-speed sputtering film formation is applied with high power, and that does not cause cracking during manufacturing of the sputtering target. As a result, (a) a conventional sputtering target for forming a ferroelectric film contains about 80 to 200 ppm of a sulfur component, and the crack and peeling during the high-speed sputtering film formation are largely affected by the sulfur component. Therefore, the sulfur component contained in the ferroelectric film-forming sputtering target is preferably as small as possible, and S: 50 pp
(b) Commercially available Ba carbonate powder and Sr carbonate powder used as a raw material powder of a conventional sputtering target for forming a ferroelectric film contain a sulfur component of 80 ppm or more. Ingredient is 80p
When a sputtering target for forming a ferroelectric film is manufactured using Ba carbonate carbonate powder and Sr carbonate carbonate powder contained at least pm, cracks occur due to hot pressing during the production of the sputtering target. The components should be as small as possible, S: 5
(C) Commercially available oxidized T must be suppressed to 0 ppm or less.
i powder has a very low sulfur content of 5 pp
m, it was found that a commercially available Ti oxide powder can be used as a raw material powder as it is.
【0008】この発明は、かかる知見に基づいて成され
たものであって、(1)S含有量が50ppm以下のB
aTi複合酸化物からなるペロブスカイト構造を有する
強誘電体膜形成用スパッタリングターゲット。(2)原
料粉末として炭酸Ba粉末および酸化Ti粉末を用意
し、これら炭酸Ba粉末および酸化Ti粉末を混合し、
得られた混合粉末を大気中で予備焼結して予備焼結体を
作製し、得られた予備焼結体を粉砕してBaTi複合酸
化物粉末を作製し、このBaTi複合酸化物粉末をホッ
トプレスしたのち機械加工することによりBaTiの複
合酸化物からなるペロブスカイト構造を有する強誘電体
膜形成用スパッタリングターゲットを製造する方法にお
いて、前記原料粉末の炭酸Ba粉末として、S含有量が
50ppm以下の炭酸Ba粉末を使用する強誘電体膜形
成用スパッタリングターゲットの製造方法、(3)S含
有量が50ppm以下のSrTi複合酸化物からなるペ
ロブスカイト構造を有する強誘電体膜形成用スパッタリ
ングターゲット、(4)原料粉末として炭酸Sr粉末お
よび酸化Ti粉末を用意し、これら炭酸Sr粉末および
酸化Ti粉末を混合し、得られた混合粉末を大気中で予
備焼結して予備焼結体を作製し、得られた予備焼結体を
粉砕してSrTi複合酸化物粉末を作製し、このSrT
i複合酸化物粉末をホットプレスしたのち、機械加工し
てSrTi複合酸化物からなるペロブスカイト構造を有
する強誘電体膜形成用スパッタリングターゲットを製造
する方法において、前記原料粉末の炭酸Sr粉末とし
て、S含有量が50ppm以下の炭酸Sr粉末を使用す
る強誘電体膜形成用スパッタリングターゲットの製造方
法、(5)S含有量が50ppm以下のBaSrTi複
合酸化物からなるペロブスカイト構造を有する強誘電体
膜形成用スパッタリングターゲット、(6)原料粉末と
して炭酸Ba粉末、炭酸Sr粉末および酸化Ti粉末を
用意し、これら炭酸Ba粉末、炭酸Sr粉末および酸化
Ti粉末を混合し、得られた混合粉末を大気中で予備焼
結して予備焼結体を作製し、得られた予備焼結体を粉砕
してBaSrTi複合酸化物粉末を作製し、このBaS
rTiの複合酸化物粉末をホットプレスしたのち、機械
加工してBaSrTi複合酸化物からなるペロブスカイ
ト構造を有する強誘電体膜形成用スパッタリングターゲ
ットを製造する方法において、前記原料粉末の炭酸Ba
粉末および炭酸Sr粉末として、いずれもS含有量が5
0ppm以下の炭酸Ba粉末および炭酸Sr粉末を使用
する強誘電体膜形成用スパッタリングターゲットの製造
方法、に特徴を有するものである。[0008] The present invention has been made based on such knowledge, and (1) B having an S content of 50 ppm or less.
A sputtering target for forming a ferroelectric film having a perovskite structure made of an aTi composite oxide. (2) Ba carbonate carbonate powder and Ti oxide powder are prepared as raw material powders, and these Ba carbonate powder and Ti oxide powder are mixed,
The obtained mixed powder is pre-sintered in the air to produce a pre-sintered body, the obtained pre-sintered body is pulverized to produce a BaTi composite oxide powder, and this BaTi composite oxide powder is In a method for producing a sputtering target for forming a ferroelectric film having a perovskite structure composed of a BaTi composite oxide by pressing and then machining, the carbon powder having an S content of 50 ppm or less is used as the carbon dioxide Ba powder of the raw material powder. Method for producing ferroelectric film forming sputtering target using Ba powder, (3) Sputtering target for forming ferroelectric film having perovskite structure comprising SrTi composite oxide having S content of 50 ppm or less, (4) Raw material Prepare Sr carbonate powder and Ti oxide powder as powder and mix these Sr carbonate powder and Ti oxide powder. And, mixed powder thus obtained was preliminarily sintered in the atmosphere to produce a pre-sintered body was pulverized and the resulting pre-sintered body to prepare a SrTi composite oxide powder, the SrT
In a method for producing a ferroelectric film-forming sputtering target having a perovskite structure composed of a SrTi composite oxide after hot pressing the i-composite oxide powder, the method further comprises: Method for producing a ferroelectric film-forming sputtering target using Sr carbonate powder having an amount of 50 ppm or less, (5) Sputtering for forming a ferroelectric film having a perovskite structure comprising a BaSrTi composite oxide having an S content of 50 ppm or less A target, (6) Ba carbonate powder, Sr carbonate powder and Ti oxide powder are prepared as raw material powders, and these Ba powder, Sr carbonate powder and Ti oxide powder are mixed, and the obtained mixed powder is pre-fired in air. To form a pre-sintered body, and pulverize the obtained pre-sintered body to obtain a BaSrTi composite. And forming the oxide powder, the BaS
hot pressing the composite oxide powder of rTi, followed by machining to produce a sputtering target for forming a ferroelectric film having a perovskite structure composed of a BaSrTi composite oxide;
Both powder and Sr carbonate powder have an S content of 5
A method of manufacturing a sputtering target for forming a ferroelectric film using 0 ppm or less Ba carbonate powder and Sr carbonate powder.
【0009】ターゲットに含まれるS含有量は、高出力
スパッタリング中のターゲットの割れおよび剥離に大き
く影響を及ぼすところから、可及的に少ない方が好まし
いが、50ppmを越えて含有すると、高出力スパッタ
リング中の全てのターゲットに割れおよび剥離が発生す
るので好ましくない。したがって、Sの含有量を50p
pm以下に定めた。S含有量の一層好ましい範囲は20
ppm以下である。The content of S contained in the target is preferably as small as possible because it greatly affects the cracking and peeling of the target during high-power sputtering. Undesirably, cracks and peeling occur in all the targets inside. Therefore, the content of S is 50 p
pm or less. A more preferred range for the S content is 20.
ppm or less.
【0010】また、この発明で使用する原料粉末である
S含有量が50ppm以下の炭酸Ba粉末は、市販の炭
酸Ba粉末を大気中、1300℃の条件で焼成し、Ba
Oと炭酸ガスに分解した後、BaOに水を作用させてB
a(OH)2 溶液を製造し、S成分をBaSO4 の化合
物の形で濾過分離した後、Ba(OH)2 溶液に炭酸ガ
スを通すことにより製造することができ、さらに、S含
有量が50ppm以下の炭酸Sr粉末は、市販の炭酸S
r粉末を大気中、1300℃の条件で焼成し、SrOと
炭酸ガスに分解した後、SrOに水を作用させてSr
(OH)2 溶液を製造し、S成分をSrSO4 の化合物
の形で濾過分離した後、Sr(OH)2 溶液に炭酸ガス
を通すことにより製造することができる。The raw material powder used in the present invention, the Ba carbonate powder having an S content of 50 ppm or less, is obtained by sintering a commercially available Ba carbonate powder in air at 1300 ° C.
After being decomposed into O and carbon dioxide, water is allowed to act on BaO
a (OH) 2 solution is produced, the S component is separated by filtration in the form of a compound of BaSO 4 , and then the solution can be produced by passing carbon dioxide gas through the Ba (OH) 2 solution. 50 ppm or less Sr carbonate powder is commercially available S carbonate
The r powder is fired in the air at 1300 ° C. to decompose it into SrO and carbon dioxide, and then water is allowed to act on the SrO to cause the SrO to decompose.
It can be produced by preparing an (OH) 2 solution, filtering and separating the S component in the form of a SrSO 4 compound, and then passing carbon dioxide gas through the Sr (OH) 2 solution.
【0011】[0011]
実施例 市販の純度:99.9%の炭酸Ba粉末を用意し、S含
有量を測定したところ、S:150ppmが含まれてい
た。この市販の純度:99.9%の炭酸Ba粉末を、大
気中、温度:1300℃の条件で焼成し、BaOと炭酸
ガスに分解した後、BaOに水を作用させてBa(O
H)2 溶液を製造し、BaSO4 の化合物を濾過分離し
た後、このBa(OH)2 溶液に炭酸ガスを通すことに
よりS含有量:20ppmの極低硫黄BaCO3 粉末を
製造した。Example A commercially available Ba carbonate powder having a purity of 99.9% was prepared, and the S content was measured. As a result, S: 150 ppm was contained. This commercially available Ba carbonate powder having a purity of 99.9% is calcined in the atmosphere at a temperature of 1300 ° C. to decompose it into BaO and carbon dioxide gas.
An H) 2 solution was produced, and the BaSO 4 compound was separated by filtration. Then, carbon dioxide gas was passed through the Ba (OH) 2 solution to produce an ultra-low sulfur BaCO 3 powder having an S content of 20 ppm.
【0012】さらに、市販の純度:99.9%の炭酸S
r粉末を用意し、S含有量を測定したところ、S:10
0ppmが含まれていた。この市販の純度:99.9%
の炭酸Sr粉末を、大気中、温度:1300℃の条件で
焼成し、SrOと炭酸ガスに分解した後、SrOに水を
作用させてSr(OH)2 溶液を製造し、SrSO4の
化合物を濾過分離した後、このSr(OH)2 溶液に炭
酸ガスを通すことによりS含有量:10ppmの極低硫
黄SrCO3 粉末を製造した。Further, commercially available purity: 99.9% of carbonic acid S
r powder was prepared and the S content was measured.
0 ppm was contained. Commercial purity: 99.9%
Carbonate Sr powder, atmospheric, temperature and fired under the conditions of 1300 ° C., after decomposing the SrO and carbon dioxide, by the action of water on the SrO manufactures Sr (OH) 2 solution, the compound of SrSO 4 After filtration and separation, carbon dioxide gas was passed through the Sr (OH) 2 solution to produce an ultra-low sulfur SrCO 3 powder having an S content of 10 ppm.
【0013】さらに原料粉末として市販のTiO2 粉末
(S含有量:5ppm未満)も用意した。Further, a commercially available TiO 2 powder (S content: less than 5 ppm) was also prepared as a raw material powder.
【0014】これら精製された極低硫黄のBaCO3 粉
末、SrCO3 粉末およびTiO2粉末を所定割合に配
合し、YSZ製ボールとともにボールミルに入れて混合
し、得られた混合粉末を大気中、1100℃で1時間保
持の条件で焼成しすることにより極低硫黄複合酸化物を
作製した。The purified ultra-low sulfur BaCO 3 powder, SrCO 3 powder and TiO 2 powder are blended in a predetermined ratio, put into a ball mill together with a YSZ ball, and mixed. By firing at a temperature of 1 ° C. for one hour, an extremely low sulfur composite oxide was produced.
【0015】この極低硫黄複合酸化物をボールミルに入
れて粉砕し、平均粒径:1〜5μmを有する極低硫黄複
合酸化物粉末を製造し、さらに得られた極低硫黄複合酸
化物粉末をグラファイトモールドに充填し、 昇温速度:5℃/min、 加熱温度:1300℃、 圧力:150ton/cm2 、 保持時間:1時間、 冷却:炉冷、 の条件でホットプレスすることにより、直径:300m
m、厚さ:5mmの寸法を有する本発明スパッタリング
ターゲット(以下、本発明ターゲットという)1〜5を
作製した。これら本発明ターゲット1〜5のS含有量を
表1に示す。The ultra-low sulfur composite oxide is pulverized in a ball mill to produce an ultra-low sulfur composite oxide powder having an average particle diameter of 1 to 5 μm. Filling in a graphite mold, heating rate: 5 ° C./min, heating temperature: 1300 ° C., pressure: 150 ton / cm 2 , holding time: 1 hour, cooling: furnace cooling, hot pressing under the following conditions: 300m
m, thickness: 5 mm of the present invention sputtering target (hereinafter referred to as the present target) were produced. Table 1 shows the S content of these inventive targets 1 to 5.
【0016】さらに、本発明ターゲット1〜5につい
て、同一原料で3回ずつホットプレスを行って割れが発
生せずにホットプレスできたターゲットの成功枚数を測
定し、その結果を表1に示した。次に、割れが発生せず
にホットプレスできたターゲットをIn−Snはんだに
より水冷銅板に接合し、高周波マグネトロンスパッタ装
置内にセットし、 雰囲気ガス:Arと酸素の混合ガス(Ar:O=1:
1)、 雰囲気圧力:1pa、 周波数:13.56Mhz、 出力:6000W、 時間:50時間、 の条件にてスパッタし、ターゲットに鱗片状に割れが発
生したか否かを黙視にて観察し、その結果も表1に示し
た。Further, for the targets 1 to 5 of the present invention, hot pressing was performed three times with the same raw material, and the number of successful targets which could be hot pressed without cracking was measured. The results are shown in Table 1. . Next, the target that could be hot pressed without cracking was bonded to a water-cooled copper plate with In-Sn solder, set in a high-frequency magnetron sputtering apparatus, and an atmosphere gas: a mixed gas of Ar and oxygen (Ar: O = 1) :
1) Atmospheric pressure: 1 pa, frequency: 13.56 Mhz, output: 6000 W, time: 50 hours, sputtered, and observed whether or not a flake-like crack was generated on the target by silent observation. The results are also shown in Table 1.
【0017】従来例 実施例で用意した市販のBaCO3 粉末、SrCO3 粉
末およびTiO2 粉末をそのまま配合し、混合し、焼成
して複合酸化物粉末を作製し、この複合酸化物粉末を粉
砕して得られた粉砕粉末を実施例と同じ条件でホットプ
レスすることにより従来スパッタリングターゲット(以
下、従来ターゲットという)1〜5を作製した。得られ
た従来ターゲット1〜5に含まれるS含有量を測定し、
同一原料で3回ずつ行いって割れが発生せずにホットプ
レスできたターゲットの成功枚数を測定し、さらに割れ
が発生せずにホットプレスできたターゲットを用いて実
施例と同じ条件でスパッタし、その際にターゲットに鱗
片状割れが発生したか否かを黙視にて観察し、その結果
を表1に示した。Conventional Example The commercially available BaCO 3 powder, SrCO 3 powder and TiO 2 powder prepared in the examples were directly blended, mixed and fired to produce a composite oxide powder, and this composite oxide powder was pulverized. By hot pressing the pulverized powder obtained as described above under the same conditions as in the examples, conventional sputtering targets (hereinafter referred to as conventional targets) 1 to 5 were produced. The S content contained in the obtained conventional targets 1 to 5 was measured,
The number of successful targets that could be hot-pressed without cracking by measuring three times with the same raw material was measured. At that time, whether or not flaky cracks occurred in the target was observed by visual observation, and the results are shown in Table 1.
【0018】[0018]
【表1】 [Table 1]
【0019】[0019]
【発明の効果】表1に示される結果から、精製されたS
含有量:20ppmのBaCO3 粉末、S含有量:10
ppmのSrCO3 粉末およびTiO2 粉末を使用して
得られたS含有量:50ppm以下の本発明ターゲット
1〜5は、いずれも市販のSを150ppm含むBaC
O3 粉末、Sを100ppm含むSrCO3 粉末および
TiO2 粉末を使用して得られたS含有量:60ppm
以上の従来ターゲット1〜5に比べて、ホットプレスに
より割れが発生せず、またスパッタリング時に剥離また
は割れが生ずることのなく高出力および高速成膜がで
き、産業上優れた効果を奏するものである。According to the results shown in Table 1, the purified S
Content: 20 ppm BaCO 3 powder, S content: 10
Each of the targets 1 to 5 of the present invention having an S content of 50 ppm or less obtained by using SrCO 3 powder and TiO 2 powder of 1.5 ppm each contains commercially available BaC containing 150 ppm of S.
S content obtained using O 3 powder, SrCO 3 powder containing 100 ppm of S and TiO 2 powder: 60 ppm
Compared to the above conventional targets 1 to 5, cracking does not occur by hot pressing, and high output and high speed film formation can be performed without peeling or cracking during sputtering, and an industrially superior effect is achieved. .
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI H01L 27/108 (58)調査した分野(Int.Cl.7,DB名) C23C 14/00 - 14/58 C04B 35/42 - 35/51 C01G 23/00 C01G 25/00 - 57/00 C01F 11/16 C01B 13/16 H01L 21/316 H01L 21/8242 H01L 27/108 JICSTファイル(JOIS)──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 7 identification code FI H01L 27/108 (58) Investigated field (Int.Cl. 7 , DB name) C23C 14/00-14/58 C04B 35/42 -35/51 C01G 23/00 C01G 25/00-57/00 C01F 11/16 C01B 13/16 H01L 21/316 H01L 21/8242 H01L 27/108 JICST file (JOIS)
Claims (6)
Tiの複合酸化物からなるペロブスカイト構造を有する
強誘電体膜形成用スパッタリングターゲット。1. A sputtering target for forming a ferroelectric film having a perovskite structure comprising a composite oxide of Ba and Ti having an S content of 50 ppm or less.
Ti粉末を用意し、これら炭酸Ba粉末および酸化Ti
粉末を混合し、得られた混合粉末を大気中で予備焼結し
て予備焼結体を作製し、得られた予備焼結体を粉砕して
BaおよびTiの複合酸化物粉末を作製し、このBaお
よびTiの複合酸化物粉末をホットプレスしたのち機械
加工することによりBaおよびTiの複合酸化物からな
るペロブスカイト構造を有する強誘電体膜形成用スパッ
タリングターゲットを製造する方法において、 前記原料粉末の炭酸Ba粉末として、S含有量が50p
pm以下の炭酸Ba粉末を使用することを特徴とする強
誘電体膜形成用スパッタリングターゲットの製造方法。2. A powder of Ba carbonate and a powder of Ti oxide are prepared as raw material powders.
The powders are mixed, the obtained mixed powder is pre-sintered in the air to produce a pre-sintered body, and the obtained pre-sintered body is pulverized to produce a Ba and Ti composite oxide powder, The method for producing a sputtering target for forming a ferroelectric film having a perovskite structure comprising a composite oxide of Ba and Ti by hot-pressing and then machining the composite oxide powder of Ba and Ti, S content 50p as Ba carbonate powder
A method for manufacturing a sputtering target for forming a ferroelectric film, comprising using a Ba carbonate powder having a particle diameter of not more than pm.
Tiの複合酸化物からなるペロブスカイト構造を有する
強誘電体膜形成用スパッタリングターゲット。3. A sputtering target for forming a ferroelectric film having a perovskite structure comprising a composite oxide of Sr and Ti having an S content of 50 ppm or less.
Ti粉末を用意し、これら炭酸Sr粉末および酸化Ti
粉末を混合し、得られた混合粉末を大気中で予備焼結し
て予備焼結体を作製し、得られた予備焼結体を粉砕して
SrおよびTiの複合酸化物粉末を作製し、このSrお
よびTiの複合酸化物粉末をホットプレスしたのち、機
械加工してSrおよびTiの複合酸化物からなるペロブ
スカイト構造を有する強誘電体膜形成用スパッタリング
ターゲットを製造する方法において、 前記原料粉末の炭酸Sr粉末として、S含有量が50p
pm以下の炭酸Sr粉末を使用することを特徴とする強
誘電体膜形成用スパッタリングターゲットの製造方法。4. An Sr carbonate powder and a Ti oxide powder are prepared as raw material powders.
The powders are mixed, the obtained mixed powder is pre-sintered in the air to produce a pre-sintered body, and the obtained pre-sintered body is pulverized to produce a composite oxide powder of Sr and Ti, After hot pressing the composite oxide powder of Sr and Ti, it is machined to produce a sputtering target for forming a ferroelectric film having a perovskite structure composed of a composite oxide of Sr and Ti. As Sr carbonate powder, S content is 50p
A method for manufacturing a sputtering target for forming a ferroelectric film, comprising using Sr carbonate powder having a particle diameter of not more than pm.
およびTiの複合酸化物からなるペロブスカイト構造を
有する強誘電体膜形成用スパッタリングターゲット、5. Ba and Sr having an S content of 50 ppm or less.
And a sputtering target for forming a ferroelectric film having a perovskite structure composed of a composite oxide of Ti and
粉末および酸化Ti粉末を用意し、これら炭酸Ba粉
末、炭酸Sr粉末および酸化Ti粉末を混合し、得られ
た混合粉末を大気中で予備焼結して予備焼結体を作製
し、得られた予備焼結体を粉砕してBa、SrおよびT
iの複合酸化物粉末を作製し、このBa、SrおよびT
iの複合酸化物粉末をホットプレスしたのち、機械加工
してBa、SrおよびTiの複合酸化物からなるペロブ
スカイト構造を有する強誘電体膜形成用スパッタリング
ターゲットを製造する方法において、 前記原料粉末の炭酸Ba粉末および炭酸Sr粉末とし
て、いずれもS含有量が50ppm以下の炭酸Ba粉末
および炭酸Sr粉末を使用することを特徴とする強誘電
体膜形成用スパッタリングターゲットの製造方法。6. A powder of Ba carbonate and Sr carbonate as raw material powders.
A powder and a Ti oxide powder were prepared, and these Ba carbonate powder, Sr carbonate powder and Ti oxide powder were mixed, and the obtained mixed powder was pre-sintered in the atmosphere to produce a pre-sintered body. Ba, Sr and T
i, a composite oxide powder of Ba, Sr and T
i. A method for producing a ferroelectric film-forming sputtering target having a perovskite structure comprising a composite oxide of Ba, Sr, and Ti after hot pressing the composite oxide powder of i. A method for producing a sputtering target for forming a ferroelectric film, wherein a Ba carbonate powder and a Sr carbonate powder each having an S content of 50 ppm or less are used as the Ba powder and the Sr carbonate powder.
Priority Applications (3)
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JP08040860A JP3127820B2 (en) | 1996-02-28 | 1996-02-28 | Sputtering target for forming ferroelectric film and method for manufacturing the same |
TW085116344A TW343999B (en) | 1996-02-28 | 1996-12-31 | High density sputtering target for forming ferroelectric film |
KR1019970006270A KR100494610B1 (en) | 1996-02-28 | 1997-02-27 | High-Density Sputtering Target for Forming High-Dielectric Films |
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JP08040860A JP3127820B2 (en) | 1996-02-28 | 1996-02-28 | Sputtering target for forming ferroelectric film and method for manufacturing the same |
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JPH09235667A JPH09235667A (en) | 1997-09-09 |
JP3127820B2 true JP3127820B2 (en) | 2001-01-29 |
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